SINGLE WALL CARBON NANOTUBES A UNIQUE ADDITIVE FOR ELECTRICALLY CONDUCTIVE

PLASTICSMPG SEMINAR 28TH NOVEMBER 2016

Michael EnotiadesEuropean Sales Manager

Office: +352 661 2799 0373Mobile: +352 661 184 007

michael.enotiades@ocsial.com

CONTENTS

OCSiAl

Single Wall Carbon Nanotubes

SWCNT in thermoplastics

OCSiAl products

Summary and path forward

1

2

3

4

5

ABOUT OCSiAl1

2009Founded to develop scalable synthesis of single wall carbon nanotubes (SWCNT)

2013Award patent for scalable SWCNT production

Launched Graphetron V1.0 nanotube reactor10 T/Y capacity

2014Began large scale industrial sampling

2016260+ people, 30 Ph.D.

Product lines for batteries, plastics, composites, coatings, elastomers

10 TONS/YR OUTPUT90% of Global SWCNT Production

4,200 m2

FACILITY

1 OCSiAl PRODUCTION FACILITYGRAPHETRON V1.0 SWCNT REACTOR

OCSiAl GROUP WORLDWIDE

Sunnyvale,CA

Incheon

Luxembourg

MoscowNovosibirskColumbus,

OH

Shenzhen,Hong-KongMumbai

1

CONTENTS

OCSiAl

Single Wall Carbon Nanotubes

SWCNT in thermoplastics

OCSiAl products

Summary and path forward

1

2

3

4

5

SINGLE WALL CARBON NANOTUBES(SWCNT)

Diameter 1.5-2.0 nm

Length > 5 μm

Wall thickness 1 atom

2

Thermal stability

Strongerthan steel

Surface area The highest length to diameter ratio

One ofthe best conductorsin the world

up to

1000 °C100 times

1g =2 basketball

courts

several

thousand times

5 timeslighter than copper

TUBALL™SWCNT WITH EXCEPTIONAL PROPERTIES

2

CONCENTRATION OFPARTICLES ~0.1%

0,5 mm

NANOFIBERS SWCNTMICROPARTICLES

A B C

0,5 mm

0,5 mm

0,5 mm

0,5 mm

0,5 mm

0,5 mm

0,5 mm0,5 mm

1

1

11

1 0 1 0 1 0

00

00

00

11

2 TUBALL™FORMS ITS OWN CONDUCTIVE 3D NETWORKAT ULTRA LOW CONCENTRATIONS

2

CONDUCTIVE CARBON BLACK

TUBALL™

TUBALL™ VS. CARBON BLACK

2

1 um

MWCNT TUBALL™

200 um200 um

1 um

MWCNT TUBALL™

TUBALL™ VS. MWCNT

CONTENTS

OCSiAl

Single Wall Carbon Nanotubes

SWCNT in thermoplastics

OCSiAl products

Summary and path forward

1

2

3

4

5

INSULATIVE

ANTISTATIC

DISSIPATIVE

CONDUCTIVE

Metals

Standard Plastics

CONDUCTIVE PLASTICS

in ESD applications

1014

1012

1010

108

106

104

102

1

10-2

10-4

10-14

10-12

10-10

10-8

10-6

10-4

10-2

1

102

104

Resistivity(W cm)

Conductivity(S/cm)

3 TUBALL™ CONDUCTIVITY RANGES

Solution Mixing Melt Mixing In Situ Polymerization

© 2013 Beyou et al.; licensee InTech.

3 TUBALL™ INCORPORATION METHODS

1. Preparation of a MB at 2% CNT

2. Masterbatch dilution on twin screw for compounds preparation

3

Twin screw

DISPERSION THROUGH 2 STEPS PROCESS

TUBALL™ MELT MIXING APPROACHFOCUS ON POLYOLEFINS

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

1.0E+08

0 0.05 0.1 0.15 0.2 0.25

Volu

me r

esis

tivity,

Wc

m

TUBALL single wall carbon nanotubes, %

CONCEPT VALIDATION ON MICROCOMPOUNDER

Percolation is observed at very low dosages

3 TUBALL™ IN POLYPROPYLENE

PROCESS OPTIMIZATION ENABLES CONDUCTIVE COMPOUNDS AT LOW DOSAGE

3

Berstorff ZE-25: 25mm co-rotating, L/D 48

TUBALL™ IN POLYPROPYLENE

3 TUBALL™ IN POLYPROPYLENE

3

1.0E+03

1.0E+05

1.0E+07

1.0E+09

1.0E+11

1.0E+13

1.0E+15

Low T° (MB andCmpd)

High T° (MB andCmpd)

Influence of Process temperature

0,1% CNT 0,2% CNT

Vo

lum

e re

sist

ivit

y(o

hm

*cm

)

Higher Temperature tends toreduce the Van de Waalsinteractions between the tubes.

High temperature reducesviscosity of molten polymer,facilitating incorporation.

Low T° : 220°C High T° : 250°C

TUBALL™ IN POLYPROPYLENE

Target a High Specific Mechanical Energy during compounding:

– High ratio/amount of kneading elements

– High screw speed

– Decrease output rate

– Optimize processing temperature

3 TUBALL™ IN POLYPROPYLENE

GENERAL GUIDELINES FOR MASTERBATCH PREPARATION

3 CONDUCTIVITY IN POLYOLEFINS

TASK: Achieve less than 104 Ohm.cm resistivity, while maintaining a tensilestrength of 12 MPa and an elongation at break of 70-200%IDEAS: Hybrid carbon black and TUBALLTM system

40 wt.% Carbon blackConductive

10-20 wt.% Carbon black+ 0,2 wt.% TUBALL

Decreasing physical-mech. properties

Impossible to use PE Possible to use PE

3

PRELIMINARY RESULTS – Property modification

CONDUCTIVITY IN POLYOLEFINS

Tuball (%) CB (%) Polymer R (Ohm.cm) Tensile strength (MPa)

Elongation at break (%)

0.2 24 LDPE 103 14 120

3

1.0E+02

1.0E+04

1.0E+06

1.0E+08

1.0E+10

1.0E+12

1.0E+14

LLDPE HDPE LDPE

Masterbatch of 2% TUBALL™diluted in MFI 20 resin

0,05 % CNT 0,1% CNT 0,2% CNT

VR

Oh

m.c

m

Haake Polylab PTW 16/40, 16 mm co-rotating, L/D 40

TUBALL™ IN POLYETHYLENECONDUCTIVE POLYETHYLENES OBTAINED AT LOW CNT DOSAGE

CONTENTS

OCSiAl

Single Wall Carbon Nanotubes

SWCNT in thermoplastics

OCSiAl products

Summary and path forward

1

2

3

4

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SPECIFICATION VALUE

CARBON CONTENT, wt. % >85

CNT, wt. % ≥75

NUMBER OF LAYERS CNT 1-2

OUTER MEAN DIAMETER CNT, nm 1.8±0.4

LENGTH OF CNT, μm >5

METAL IMPURITIES, wt. % <15

Certificate of analysis by Intertek#: IWTN/COA/W663/001 (14 May 2014)

4

TUBALLTM

Dosage

Melt flow index

at 230°C/2.16kg

(ASTM D1238)

Melting point

(ISO 11357)

Real density

(internal

method)

Moisture

content

(at packaging)

2 wt. % 10 g/10 min 165 °С 918 kg/m3 < 0.01% ppm

Primary characteristics of TUBALLTM PLAST_E PP

Primary characteristics of TUBALLTM PLAST_E PE

TUBALLTM

Dosage

Melt flow index

at 190°C/2.16kg

(ASTM D1238)

Melting point

(ISO 11357)

Real density

(internal

method)

Moisture

content

(at packaging)

2 wt. % 2.9 g/10 min 127 °С 941 kg/m3 < 0.01% ppm

PLAST_E MASTERBATCHESDEMONSTRATORS FOR POLYOLEFINS

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

1.0E+08

0 0.5 1 1.5 2 2.5 3

Su

rfa

ce

re

sis

tivity,

Ω/s

q

TUBALL™ MATRIX 202, wt.%

Incorporation approach

MATRIX 202 FOR SOFT PVCDEVELOPMENTAL GRADE

4

CONTENTS

OCSiAl

Single Wall Carbon Nanotubes

SWCNT in thermoplastics

OCSiAl products

Summary and path forward

1

2

3

4

5

5 SUMMARY

1. OCSiAl has developed a continuous, high volume process for producing

nanotubes.

2. TUBALL™ is a high quality, very conductive single wall carbon nanotube

product.

3. TUBALL™ can be incorporated in thermoplastics through melt mixing.

4. Conductive networks can be created in polymer matrices at

low TUBALL™ dosages without compromising properties.

5. More solutions for thermoplastics are under development.

5 REACH (EU) AND EPA (USA)

1. Tuball is compliant in the EU for

commercial sales up to 1 T/Y

2. REACH application for up to 10 T/Y has

been achieved. File number

01-2120130006-75-0000

3. OCSiAl is in the final stages of preparing

PMN for EPA

OCSiAl GROUPRedefining materials

Reinventing technologies

THANK YOU FOR YOUR ATTENTION !